EP1781745A2 - Dispersions colloidales metalliques et leurs encres metalliques aqueuses - Google Patents
Dispersions colloidales metalliques et leurs encres metalliques aqueusesInfo
- Publication number
- EP1781745A2 EP1781745A2 EP05818402A EP05818402A EP1781745A2 EP 1781745 A2 EP1781745 A2 EP 1781745A2 EP 05818402 A EP05818402 A EP 05818402A EP 05818402 A EP05818402 A EP 05818402A EP 1781745 A2 EP1781745 A2 EP 1781745A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- printing
- silver
- dispersant
- hydrophilic segments
- ink
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
- C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
Definitions
- This invention relates to colloid dispersions of elemental metal, or its alloy, such as silver, and inks having metal for printing or other applications of the metal.
- aqueous metal dispersions Two ways appear known to make the aqueous metal dispersions.
- the physical method is to directly disperse the metal in the presence of a dispersing agent with high energy.
- Another method also widely used is the chemical reduction method.
- silver salts can be reduced to silver metal by chemical reducing reagents.
- Commonly used reducing reagents are borohydrides, citrate salts; ascorbic acid, hydrazine, glucose, hydrocarbons and hydrogen. Therefore, using this approach to prepare metal colloid in the aqueous medium has great convenience and advantage.
- CMC carboxymethyl cellulose sodium salt
- WO O3/O38OO2A1 uses the CMC as the stabilizer and the citric acid presidium salt as the reducing reagent.
- High molecular weight CMC could increase the viscosity of the dispersion.
- Carboxylic groups is not compatible with the silver salt in the reduction system, so the concentration of the silver and the number of the carboxylic groups are very sensitive in the reaction. This method introduces a large amount of salts into the system, which not only limits its selection of the stabilizing reagent, also final remove of the excess salt is required to render the system compatible with the ink jet printing. The reduction has to be finished at high temperature, also limited the equipment and increased the cost.
- This invention employs the chemical reduction in an aqueous medium of a metal salt to the elementary metal colloid in the presence of a polymeric dispersant for the
- the polymeric dispersants have ionic hydrophilic segments and nonionic hydrophilic segments.
- Such a dispersion is employed in aqueous inkjet inks having standard ingredients, particularly a humectant to reduce evaporation.
- the inks when printed on an absorptive substrate leave silver which is sintered by heat to a
- the polymeric dispersant may be somewhat made like dispersants which have been developed in recent years for the pigmented inks in inkjet. But there are also some fundamental differences. It is preferred that the dispersant is an acrylic polymer contains at least two major components: anionic segments and non-ionic segments.
- the anionic segments contains monomer having the carboxylic acid or sulfonic acid functional groups, which provides the electrostatic stability of the dispersion.
- the acid groups also provide the ability of interaction between silver and the polymer.
- the non- ionic segments are chosen from the hydroxy terminated polyethylene glycol monomers. It not only provides the steric stabilization, the hydrogen bonding interaction with the silver, but also give the solubility of the dispersion in the water/organic solvent therefore provides the ink printing reliability.
- the PEG monomer has a molecular weight lower than 1000.
- the polymer is a random co- or ter-polymer made through free radical polymerization.
- the molecular weight is controlled by a chain transfer reagent. Any kind of mercaptan compound can be used as the chain transfer reagent.
- Preferred chain transfer reagent in this reaction contains the hydroxy or acid functionality, such as 2- mercaptoethanol, 3-mercaptoethanol, mercaptoacetic acid, mercaptopropionic acid. 3- mercapto- 1 ,2-propanediol.
- the carboxylic acid content is very important in the dispersion. Too less will not provide the stability of the colloid preferred. Too much will also not compatible with the silver salt and result in large metal particle formation. The actual content can be judged in the reduction.
- the molecular weight is a not very important factor, and can be judged by the art in the term of dispersant and ink jet printing reliability. Too high molecular weight will increase the viscosity of the ink. But too low will not provide the stability of the dispersion also. Preferable from 8000 to 1000 by weight average molecular weight.
- the reducing reagent used here is hydrazine. According to the general equation: 4Ag+ + N2H4 — »4Ag + N2 + 4H+ ( J. Appl. Polym. Sci. 1992, Vol. 44, pages
- the reaction is very simple and can be completed at room temperature.
- the bi-product is a gas, which made the final product easy to be purified. Because of the existence of the stabilizer, the concentration of the silver can also be adjusted in the process.
- the particle size of the silver colloid is controlled by several factors.
- First is the dispersant.
- the acid functions to interact and stabilize the silver colloid. But the quantity of the acid groups directly influence the solubility of the silver salt, and the solubility of the silver salt affects the particle size. The best quantity of the acid is that it will form a clear solution with the silver nitrate. If the clouds form, the particle size of the silver will be higher than expected.
- Second is the process. This reaction's bi-product is a gas. ft generates foam in the reaction. Therefore, control the stirring speed, the addition speed and the ratio of the silver salt and the hydrazine is very important.
- the silver salt/dispersant solution and the hydrazine be dropped simultaneously to a dispersant solution.
- the dropping speed is silver salt faster than hydrazine.
- the last thing is the amount of the dispersant. Although it looked like the quantity of the dispersant is not very important in the particle size formation period, to maintain its stability through out the shelf life.
- Preferred ratio of dispersant to silver nitrate is 0.1 to 1 to 0.6 to 1 by weight. Most preferred is 0.2 to 1 by weight.
- Some commercial polymers have the ability to disperse the silver colloid particles, such as polyacrylic acid. But, to reach the required particle size, the concentration, the required storage stability and the thermal ink print head reliability, this embodiment employs selected the monomer for this unique purpose.
- PAA polyacrylic acid
- the random co-polymer of methacrylic acid and polyethylene glycol methacrylate (MAA/PEGMA); and co-polymer of MAA/Tris (polyethyleneglycol)2,4,6-tris 1-phenylethylphenylether methacrylate), are used here.
- MAA/PEGMA polyethylene glycol methacrylate
- MAA/Tris polyethyleneglycol2,4,6-tris 1-phenylethylphenylether methacrylate
- the general methods of synthesis of the co-polymers are as follows: A mixture of polyethylene glycol methacrylate (mw360) 54g and methacrylic acid 8g, 3-mercapto-l ,2-propanediol 2.Og , iso-propanol 100ml and V-601 (dimethyl 2,2'-azobisisobutyrate) 0.2g is mixed in a 300ml three neck round bottom flask equipped with a mechanical stir, condenser and thermometer. The flask equipment is
- Tr is 50
- An illustrative ink formulation used for printing is as follows: The particle size
- the silver is preferred between 10 to 30nm.
- Silver content of this ink is 13.5% by Inductive Coupled Plasma (ICP) measurement.
- ICP Inductive Coupled Plasma
- Particle size is 16nm; viscosity is 2.2cp; pH is adjusted with a base to 6.0.
- Printing may be on the coated surface of commercially available papers for
- Process can be variable, include print pass (i.e., how many 600dpi layers are laid on the media), print mode (full density vs. shingling mode), sinter temperature and sinter time.
- print pass i.e., how many 600dpi layers are laid on the media
- print mode full density vs. shingling mode
- sinter temperature sinter time.
- full density print pattern 600dpi ink drop will be laid down after one swath.
- For shingling print pattern it needs two repeat swathes to get 600dpi ink drop density. The result indicates that the
- best performance of the described ink has a sheet resistance 0.16 ⁇ / .
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Conductive Materials (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/925,042 US20060044382A1 (en) | 2004-08-24 | 2004-08-24 | Metal colloid dispersions and their aqueous metal inks |
PCT/US2005/029728 WO2006036379A2 (fr) | 2004-08-24 | 2005-08-19 | Dispersions colloidales metalliques et leurs encres metalliques aqueuses |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1781745A2 true EP1781745A2 (fr) | 2007-05-09 |
EP1781745A4 EP1781745A4 (fr) | 2008-08-27 |
Family
ID=35942464
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05818402A Withdrawn EP1781745A4 (fr) | 2004-08-24 | 2005-08-19 | Dispersions colloidales metalliques et leurs encres metalliques aqueuses |
Country Status (6)
Country | Link |
---|---|
US (1) | US20060044382A1 (fr) |
EP (1) | EP1781745A4 (fr) |
JP (1) | JP2007523258A (fr) |
KR (1) | KR20070052765A (fr) |
CN (1) | CN101080264A (fr) |
WO (1) | WO2006036379A2 (fr) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7931941B1 (en) | 2004-10-29 | 2011-04-26 | Pchem Associates, Inc. | Synthesis of metallic nanoparticle dispersions capable of sintering at low temperatures |
US20070144305A1 (en) * | 2005-12-20 | 2007-06-28 | Jablonski Gregory A | Synthesis of Metallic Nanoparticle Dispersions |
US7919015B2 (en) * | 2006-10-05 | 2011-04-05 | Xerox Corporation | Silver-containing nanoparticles with replacement stabilizer |
CA2680201A1 (fr) | 2007-03-01 | 2008-09-25 | Pchem Associates, Inc. | Blindage a partir de compositions de nanoparticules metalliques et dispositifs et procedes pour ceux-ci |
JP5125464B2 (ja) * | 2007-12-10 | 2013-01-23 | セイコーエプソン株式会社 | 導体パターン形成用インク、導体パターンおよび配線基板 |
US20100015462A1 (en) * | 2008-02-29 | 2010-01-21 | Gregory Jablonski | Metallic nanoparticle shielding structure and methods thereof |
TWI438923B (zh) | 2008-07-30 | 2014-05-21 | Epistar Corp | 光電元件製造方法 |
CN101645475B (zh) * | 2008-08-07 | 2013-01-02 | 晶元光电股份有限公司 | 发光元件及其制造方法 |
EP2204250A1 (fr) * | 2008-12-16 | 2010-07-07 | Akzo Nobel Coatings International B.V. | Dispersions aqueuses de particules d'argent |
KR101700615B1 (ko) * | 2010-03-30 | 2017-01-31 | 주식회사 동진쎄미켐 | 금속 나노입자의 제조방법, 이에 의해 제조된 금속 나노입자 및 이를 포함하는 금속 잉크 조성물 |
JP2011241241A (ja) * | 2010-05-14 | 2011-12-01 | Seiko Epson Corp | 水系インク組成物およびこれを用いた記録物 |
EP2386419B1 (fr) | 2010-05-14 | 2013-07-03 | Seiko Epson Corporation | Méthode pour l'impression à jet d'encre, et matière imprimée |
JP5949104B2 (ja) * | 2012-04-27 | 2016-07-06 | 株式会社リコー | 金属粒子分散剤、金属粒子分散インク及び導電性パターン形成方法 |
EP2781562B1 (fr) * | 2013-03-20 | 2016-01-20 | Agfa-Gevaert | Procédé pour préparer une dispersion de nanoparticules métalliques |
JP2018535321A (ja) * | 2015-10-30 | 2018-11-29 | クラリアント・インターナシヨナル・リミテツド | 高められた安定性を有する金属分散体 |
KR102307482B1 (ko) | 2020-06-05 | 2021-09-30 | 주식회사 나노와 | 고농도 금속잉크의 제조방법 및 이 방법에 의해 제조되는 고농도 금속잉크 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5085698A (en) * | 1990-04-11 | 1992-02-04 | E. I. Du Pont De Nemours And Company | Aqueous pigmented inks for ink jet printers |
EP0556649A1 (fr) * | 1992-02-20 | 1993-08-25 | E.I. Du Pont De Nemours & Company Incorporated | Dispersions aqueouses contenant des polymèrs ABC à trois blocs comme dispersants |
US5708095A (en) * | 1996-08-30 | 1998-01-13 | E. I. Du Pont De Nemours And Company | Graft copolymers containing sulfonate and phosphonate groups having particular utility as pigmented ink dispersants |
WO2003038002A1 (fr) * | 2001-11-01 | 2003-05-08 | Yissum Research Development Company Of The Hebrew University Of Jerusalem | Encres pour jet d'encre contenant des nanoparticules metalliques |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2851380A (en) * | 1953-02-09 | 1958-09-09 | Woodmont Products Inc | Conductive ink and article coated therewith |
DE69506333T2 (de) * | 1994-07-11 | 1999-07-15 | Agfa-Gevaert N.V., Mortsel | Tintenstrahldruckverfahren |
JP3594803B2 (ja) * | 1997-07-17 | 2004-12-02 | 日本ペイント株式会社 | 貴金属又は銅のコロイド溶液及びその製造方法並びに塗料組成物及び樹脂成型物 |
US6551304B1 (en) * | 1999-12-01 | 2003-04-22 | Abbeymoor Medical, Inc. | Magnetic retrieval device and method of use |
US6336966B1 (en) * | 1999-12-16 | 2002-01-08 | Ppg Industries Ohio, Inc. | Pigment dispersions containing dispersants having core and arm star architecture prepared by controlled radical polymerization |
US6893490B2 (en) * | 2000-04-17 | 2005-05-17 | Matsushita Electric Industrial Co., Ltd. | Ink for display panel and method for producing plasma display panel using the same |
US6500871B1 (en) * | 2000-06-08 | 2002-12-31 | Rhodia Chimie | Process for preparing colloids of particles coming from the hydrolysis of a salt of a metal cation |
US6660058B1 (en) * | 2000-08-22 | 2003-12-09 | Nanopros, Inc. | Preparation of silver and silver alloyed nanoparticles in surfactant solutions |
DE10317973A1 (de) * | 2002-04-18 | 2004-01-15 | Benq Corp., Kweishan | Tintenset für Tintenstrahldrucker |
-
2004
- 2004-08-24 US US10/925,042 patent/US20060044382A1/en not_active Abandoned
-
2005
- 2005-08-19 KR KR1020077004230A patent/KR20070052765A/ko not_active Application Discontinuation
- 2005-08-19 JP JP2006541521A patent/JP2007523258A/ja active Pending
- 2005-08-19 EP EP05818402A patent/EP1781745A4/fr not_active Withdrawn
- 2005-08-19 WO PCT/US2005/029728 patent/WO2006036379A2/fr active Application Filing
- 2005-08-19 CN CNA2005800015398A patent/CN101080264A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5085698A (en) * | 1990-04-11 | 1992-02-04 | E. I. Du Pont De Nemours And Company | Aqueous pigmented inks for ink jet printers |
EP0556649A1 (fr) * | 1992-02-20 | 1993-08-25 | E.I. Du Pont De Nemours & Company Incorporated | Dispersions aqueouses contenant des polymèrs ABC à trois blocs comme dispersants |
US5708095A (en) * | 1996-08-30 | 1998-01-13 | E. I. Du Pont De Nemours And Company | Graft copolymers containing sulfonate and phosphonate groups having particular utility as pigmented ink dispersants |
WO2003038002A1 (fr) * | 2001-11-01 | 2003-05-08 | Yissum Research Development Company Of The Hebrew University Of Jerusalem | Encres pour jet d'encre contenant des nanoparticules metalliques |
Non-Patent Citations (2)
Title |
---|
DATABASE WPI Week 199923 Thomson Scientific, London, GB; AN 1999-267384 XP002488693 -& JP 11 080647 A 26 March 1999 (1999-03-26) * |
See also references of WO2006036379A2 * |
Also Published As
Publication number | Publication date |
---|---|
WO2006036379A2 (fr) | 2006-04-06 |
WO2006036379A3 (fr) | 2007-05-24 |
EP1781745A4 (fr) | 2008-08-27 |
KR20070052765A (ko) | 2007-05-22 |
JP2007523258A (ja) | 2007-08-16 |
US20060044382A1 (en) | 2006-03-02 |
CN101080264A (zh) | 2007-11-28 |
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